Method of electroplating photoresist defined features from copper electroplating baths containing reaction products of pyrazole compounds and bisepoxides

ABSTRACT

Electroplating methods enable the plating of photoresist defined features which have substantially uniform morphology. The electroplating methods include copper electroplating baths with reaction products of pyrazole compounds and bisepoxides to electroplate the photoresist defined features. Such features include pillars, bond pads and line space features.

FIELD OF THE INVENTION

The present invention is directed to a method of electroplating photoresist defined features from copper electroplating baths which include reaction products of pyrazole compounds and bisepoxides. More specifically, the present invention is directed to a method of electroplating photoresist defined features from copper electroplating baths which include reaction products of pyrazole compounds and bisepoxides where the photoresist defined features have substantially uniform surface morphology.

BACKGROUND OF THE INVENTION

Photoresist defined features include copper pillars and redistribution layer wiring such as bond pads and line space features for integrated circuit chips and printed circuit boards. The features are formed by the process of lithography where a photoresist is applied to a substrate such as a semiconductor wafer chip often referred to as a die in packaging technologies, or epoxy/glass printed circuit boards. In general, the photoresist is applied to a surface of the substrate and a mask with a pattern is applied to the photoresist. The substrate with the mask is exposed to radiation such as UV light. Typically the sections of the photoresist which are exposed to the radiation are developed away or removed exposing the surface of the substrate. Depending on the specific pattern of the mask an outline of a circuit line or aperture may be formed with the unexposed photoresist left on the substrate forming the walls of the circuit line pattern or aperture. The surface of the substrate includes a metal seed layer or other conductive metal or metal alloy material which enables the surface of the substrate conductive. The substrate with the patterned photoresist is then immersed in a metal electroplating bath, typically a copper electroplating bath, and metal is electroplated in the circuit line pattern or aperture to form features such as pillars, bond pads or circuit lines, i.e., line space features. When electroplating is complete, the remainder of the photoresist is stripped from the substrate with a stripping solution and the substrate with the photoresist defined features is further processed.

Pillars, such as copper pillars, are typically capped with solder to enable adhesion as well as electrical conduction between the semiconductor chip to which the pillars are plated and a substrate. Such arrangements are found in advanced packaging technologies. Solder capped copper pillar architectures are a fast growing segment in advanced packaging applications due to improved input/output (I/O) density compared to solder bumping alone. A copper pillar bump with the structure of a non-reflowable copper pillar and a reflowable solder cap has the following advantages: (1) copper has low electrical resistance and high current density capability; (2) thermal conductivity of copper provides more than three times the thermal conductivity of solder bumps; (3) can improve traditional BGA CTE (ball grid array coefficient of thermal expansion) mismatch problems which can cause reliability problems; and (4) copper pillars do not collapse during reflow allowing for very fine pitch without compromising stand-off height.

Of all the copper pillar bump fabrication processes, electroplating is by far the most commercially viable process. In the actual industrial production, considering the cost and process conditions, electroplating offers mass productivity and there is no polishing or corrosion process to change the surface morphology of copper pillars after the formation of the copper pillars. Therefore, it is particularly important to obtain a smooth surface morphology by electroplating. The ideal copper electroplating chemistry and method for electroplating copper pillars yields deposits with excellent uniformity, flat pillar shape and void-free intermetallic interface after reflow with solder and is able to plate at high deposition rates to enable high wafer through-out. However, development of such plating chemistry and method is a challenge for the industry as improvement in one attribute typically comes at the expense of another. Copper pillar based structures have already been employed by various manufacturers for use in consumer products such as smart phones and PCs. As Wafer Level Processing (WLP) continues to evolve and adopt the use of copper pillar technology, there will be increasing demand for copper plating baths and methods with advanced capabilities that can produce reliable copper pillar structures.

Similar problems of morphology are also encountered with the metal electroplating of redistribution layer wiring. Detects in the morphology of bond pads and line space features also compromise the performance of advanced packaging articles. Accordingly, there is a need for a copper electroplating methods and chemistries which provide copper photoresist defined features where the features have substantially uniform surface morphology.

SUMMARY OF THE INVENTION

A method including: a) providing a substrate comprising a layer of photoresist, wherein the layer of photoresist comprises a plurality of apertures; b) providing a copper electroplating bath comprising one or more reaction products of one or more pyrazole compounds and one or more bisepoxides; an electrolyte; one or more accelerators; and one or more suppressors; c) immersing the substrate comprising the layer of photoresist with the plurality of apertures in the copper electroplating bath; and d) electroplating a plurality of copper photoresist defined features in the plurality of apertures, the plurality of photoresist defined features comprise an average % TIR of 0% to 10%.

Copper electroplating baths include a reaction product of one or more pyrazole compounds and one or more bisepoxides, an electrolyte, one or more sources of copper ions, one or more accelerators and one or more suppressors in sufficient amounts to electroplate copper photoresist defined features having an average % TIR of 0% to 10%.

The present invention is also directed to an array of photoresist defined features on a substrate comprising an average % TIR of 0% to 10% and a % WID of 0% to 10%.

The copper electroplating methods and baths provide copper photoresist defined features which have a substantially uniform morphology and are substantially free of nodules. The copper pillars and bond pads have a substantially flat profile. The copper electroplating baths and methods enable an average % TIR to achieve the desired morphology.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a SEM of a copper pillar at 300× electroplated from a copper electroplating bath containing a reaction product of 3,5-dimethyl pyrazole and glycerol diglycidyl ether.

FIG. 2 is a 3D image of a copper pillar electroplated from a copper electroplating bath con taming a reaction product of 3,5-dimethyl pyrazole and neopentyl glycol diglycidyl ether.

FIG. 3 is a SEM of a copper pillar at 300× electroplated from a copper electroplating bath containing a conventional leveler compound which is a reaction product of 2-methylquinolin-4-amine, 2-(2-aminoethyl)pyridine and 1,4-butanediol diglycidyl ether.

DETAILED DESCRIPTION OF THE INVENTION

As used throughout this specification the following abbreviations shall have the following meanings unless the context clearly indicates otherwise: A=amperes; A/dm²=amperes per square decimeter=ASD; ° C.=degrees Centigrade; UV=ultraviolet radiation; g=gram; ppm=parts per million=mg/L; L=liter, μm=micron=micrometer; mm=millimeters; cm=centimeters; DI=deionized; mL=milliliter; mol=moles; mmol=millimoles; Mw=weight average molecular weight; Mn=number average molecular weight; SEM=scanning electron microscope; FIB=focus ion beam; WID=within-die; UR=total indicated runout=total indicator reading=full indicator movement=FIM; RDL=redistribution layer; and Avg.=average.

As used throughout this specification, the term “plating” refers to metal electroplating. “Deposition” and “plating” are used interchangeably throughout this specification. “Accelerator” refers to an organic additive that increases the plating rate of the electroplating bath. “Suppressor” refers to an organic additive that suppresses the plating rate of a metal during electroplating. The term “array” means an ordered arrangement. The term “moiety” means a part of a molecule or polymer that may include either whole functional groups or parts of functional groups as substructures. The terms “moiety” and “group” are used interchangeably throughout the specification. The term “aperture” means opening, hole, or gap. The term “morphology” means the form, shape and structure of an article. The term “total indicator runout” or “total indicator reading” is the difference between the maximum and minimum measurements, that is, readings of an indicator, on planar, cylindrical, or contoured surface of a part, showing its amount of deviation from flatness, roundness (circularity), cylindricity, concentricity with other cylindrical features or similar conditions. The term “profilometry” means the use of a technique in the measurement and profiling of an object or the use of a laser or white light computer-generated projections to perform surface measurements of three dimensional objects. The term “pitch” means a frequency of feature positions from each other on a substrate. The term “normalizing” means a resealing to arrive at values relative to a size variable such as a ratio as % TIR. The term “average” means a number expressing the central or typical value of a parameter. The term “parameter” means a numerical or other measurable factor forming one of a set that defines a system or sets the conditions of its operation. The articles “a” and “an” refer to the singular and the plural.

All numerical ranges are inclusive and combinable in any order, except where it is clear that such numerical ranges are constrained to add up to 100%.

Methods and baths for electroplating copper photoresist defined features of the present invention enable an array of photoresist defined features having an average % TIR such that the features have a morphology which is substantially smooth, free of nodules and with respect to pillars, bond pads and line space features have substantially flat profiles. The photoresist defined features of the present invention are electroplated with photoresist remaining on the substrate and extend beyond the plane of the substrate. This is in contrast to dual damascene and printed circuit board plating which do not use photoresist to define features which extend beyond the plane of the substrate but are inlaid into the substrate. An important difference between photoresist defined features and damascene and printed circuit board features is that with respect to the damascene and printed circuit boards the plating surface including the sidewalls are all conductive. The dual damascene and printed circuit board plating baths have a bath formulation that provides bottom-up or super-conformal filling, with the bottom of the feature plating faster than the top of the feature. In photoresist defined features, the sidewalls are non-conductive photoresist and plating only occurs at the feature bottom with the conductive seed layer and proceeds in a conformal or same plating speed everywhere deposition.

While the present invention is substantially described with respect to methods of electroplating copper pillars having a circular morphology, the present invention also applies to other photoresist defined features such as bond pads and line space features. In general, the shapes of the features may be, for example, oblong, octagonal and rectangular in addition to circular or cylindrical. The methods of the present invention are preferably for electroplating copper cylindrical pillars.

The copper electroplating methods provide an array of copper photoresist defined features, such as copper pillars, with an average % TIR of 0% to 10%, preferably from 4% to 9%.

In general, the average % TIR for an array of photoresist defined features on a substrate involves determining the % TIR of individual features from the array of features on the single substrate and averaging them. Typically, the average % TIR is determined by determining the % TIR for individual features of a region of low density or larger pitch and the % TIR for individual features of a region of high density or smaller pitch on the substrate and averaging the values. By measuring the % TIR of a variety of individual features, the average % TIR becomes representative of the whole substrate.

The % TIR may be determined by the following equation:

% TIR=[height_(center)−height_(edge)]/height_(max)×100

where height_(center) is the height of a pillar as measured along its center axis and height_(edge) is the height of the pillar as measured along its edge at the highest point on the edge. Height_(max) is the height from the bottom of the pillar to its highest point on its top. Height_(max) is a normalizing factor.

Individual feature TIRs may be determined by the following equation:

TIR=height_(center)−height_(edge),

where height_(center) and height_(edge) are as defined above.

In addition, the copper electroplating methods and baths may provide an array of copper photoresist defined features with a % WID of 0% to 10%, preferably from 3% to 5%. The % WID or within-die may be determined by the following equation:

% WID=½×[(height_(max)−height_(min))/height_(avg)]×100

where height_(max) is the height of the tallest pillar of an array of pillars electroplated on a substrate as measured at the tallest part of the pillar. Height_(min) is the height of the shortest pillar of an array of pillars electroplated on the substrate as measured at the tallest part of the pillar. Height_(avg) is the average height of all of the pillars electroplated on the substrate.

Most preferably, the methods of the present invention provide an array of photoresist defined features on a substrate where there is a balance between the average % TIR and % WED such that the average % TIR ranges from 0% to 10% and the % WID ranges from 0% to 10% with the preferred range as disclosed above.

The parameters of the pillars for determining TIR, % TIR and % WID may be measured using optical profilometry such as with a white light LEICA DCM 3D or similar apparatus. Parameters such as pillar height and pitch may be measured using such devices.

In general, the copper pillars electroplated from the copper electroplating baths may have aspect ratios of 3:1 to 1:1 or such as 2:1 to 1:1. RDL type structure may have aspect ratios as large as 1:20 (height:width).

Preferably the pyrazole compounds have the following general formula:

where R₁, R₂ and R₃ are independently chosen from hydrogen, linear or branched (C₁-C₁₀)alkyl; hydroxyl; linear or branched (C₁-C₁₀)alkoxy, linear or branched hydroxy(C₁-C₁₀)alkyl; linear or branched alkoxy(C₁-C₁₀)alkyl; linear or branched, carboxy(C₁-C₁₀)alkyl; linear or branched amino(C₁-C₁₀)alkyl; substituted or unsubstituted phenyl where the substituents may be hydroxyl, hydroxy(C₁-C₃)alkyl, or (C₁-C₃)alkyl. Preferably, R₁, R₂ and R₃ are independently chosen from hydrogen; linear or branched (C₁-C₅)alkyl; hydroxyl; linear or branched hydroxy(C₁-C₅)alkyl; and linear or branched amino(C₁-C₅)alkyl. More preferably R₁, R₂ and R₃ are independently chosen from hydrogen and (C₁-C₃)alkyl such as methyl, ethyl and propyl moieties. Even more preferably R₁ and R₃ are independently chosen from hydrogen, methyl and ethyl, and R₂ is hydrogen. Most preferably R₁ and R₃ are independently chosen from methyl and ethyl and R₂ is hydrogen. Examples of such preferred compounds are pyrazole, 3-methyl pyrazole, 4-methyl pyrazole, 3,4-dimethyl pyrazole and 3,5-dimethyl pyrazole.

Preferably bisepoxides have a formula:

where R₄ and R₅ are independently chosen from hydrogen and (C₁-C₄)alkyl; R₆ and R₇ are independently chosen from hydrogen, methyl and hydroxyl; to m=1-6 and n=1-20. Preferably, R₄ and R₅ are hydrogen. Preferably R₆ and R₇ are independently chosen from hydrogen, methyl and hydroxyl. More preferably R₆ is hydrogen or hydroxyl, and R₇ is hydrogen. Preferably m=2-4 and n=1-2. More preferably m=3-4 and n=1. When m=3 and n=1, it is most preferred that at least one of R₆ is hydroxyl. When in m=4 and n=1, it is most preferred that R₆ is hydrogen.

Compounds of formula (II) include, but are not limited to, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, di(ethylene glycol) diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,3-butandiol diglycidyl ether, propylene glycol diglycidyl ether, di(propylene glycol) diglycidyl ether, poly(ethylene glycol) diglycidyl ether compounds and poly(propylene glycol) diglycidyl ether compounds. Examples of preferred compounds of formula (ill) are glycerol diglycidyl ether and neopentyl glycol diglycidyl ether.

The reaction products of the present invention can be prepared by conventional methods known in the art. Examples of methods for preparing the reaction product of a pyrazole compound and a bisepoxide are disclosed in U.S. Pat. No. 8,747,643.

The aqueous copper electroplating baths contain a source of metal ions, an electrolyte, and a reaction product of one or more pyrazole compounds and one or more bisepoxides. The aqueous copper electroplating baths also include an accelerator, a suppressor and optionally a source of halide ions. Metals which may be electroplated from the baths to form copper pillars include copper and copper/tin alloy. Preferably copper metal is electroplated.

Suitable copper ion sources are copper salts and include without limitation: copper sulfate; copper halides such as copper chloride; copper acetate; copper nitrate; copper tetrafluoroborate; copper alkylsulfonates; copper aryl sulfonates; copper sulfamate; copper perchlorate and copper gluconate. Exemplary copper alkane sulfonates include copper (C₁-C₆)alkane sulfonate and more preferably copper (C₁-C₃)alkane sulfonate. Preferred copper alkane sulfonates are copper methanesulfonate, copper ethanesulfonate and copper propanesulfonate. Exemplary copper arylsulfonates include, without limitation, copper benzenesulfonate and copper p-toluenesulfonate. Mixtures of copper ion sources may be used. One or more salts of metal ions other than copper ions may be added to the present electroplating baths. Preferably, the copper salt is present in an amount sufficient to provide an amount of copper ions of 30 to 70 g/L of plating solution. More preferably the amount of copper ions is from 40 to 60 g/L.

The electrolyte useful in the present invention may be alkaline or acidic. Preferably the electrolyte is acidic. Preferably, the pH of the electrolyte is ≦2. Suitable acidic electrolytes include, but are not limited to, sulfuric acid, acetic acid, fluoroboric acid, alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and trifluoromethane sulfonic acid, aryl sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, sulfamic acid, hydrochloric acid, hydrobromic acid, perchloric acid, nitric acid, chromic acid and phosphoric acid. Mixtures of acids may be advantageously used in the present metal plating baths. Preferred acids include sulfuric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, hydrochloric acid and mixtures thereof. The acids may be present in an amount in the range of 1 to 400 g/L. Electrolytes are generally commercially available from a variety of sources and may be used without further purification.

Such electrolytes may optionally contain a source of halide ions. Typically chloride ions and bromide ions are used. Exemplary chloride ion sources include copper chloride, tin chloride, sodium chloride, potassium chloride and hydrochloric acid. Sources of bromide ions include sodium bromide, potassium bromide and hydrogen bromide. A wide range of halide ion concentrations may be used in the present invention. Typically, the halide ion concentration is in the range of 0 to 200 ppm based on the plating bath preferably 50 ppm to 80 ppm. Such halide ion sources are generally commercially available and may be used without further purification.

The plating compositions typically contain an accelerator. Any accelerators (also referred to as brightening agents) are suitable for use in the present invention. Such accelerators are well-known to those skilled in the art. Accelerators include, but are not limited to, N,N-dimethyl-dithiocarbamic acid-(3-sulfopropyl)ester; 3-mercapto-propylsulfonic acid-(3-sulfopropyl)ester; 3-mercapto-propylsulfonic acid sodium salt; carbonic acid,dithio-O-ethylester-S-ester with 3-mercapto-1-propane sulfonic acid potassium salt; bis-sulfopropyl disulfide; bis-(sodium sulfopropyl)-disulfide; 3-(benzothiazolyl-S-thio)propyl sulfonic acid sodium salt; pyridinium propyl sulfobetaine; 1-sodium-3-mercaptopropane-1-sulfonate; N,N-dimethyl-dithiocarbamic acid-(3-sulfoethyl)ester; 3-mercapto-ethyl propylsulfonic acid-(3-sulfoethyl)ester; 3-mercapto-ethylsulfonic acid sodium salt; carbonic acid-dithio-O-ethylester-S-ester with 3-mercapto-1-ethane sulfonic acid potassium salt; bis-sulfoethyl disulfide; 3-(benzothiazoyl-S-thio)ethyl sulfonic acid sodium salt; pyridinium ethyl sulfobetaine; and 1-sodium-3-mercaptoethane-1-sulfonate. Accelerators may be used in a variety of amounts. In general, accelerators are used in an amount in a range of 0.1 ppm to 1000 ppm.

Suitable suppressors include, but are not limited to, polypropylene glycol copolymers and polyethylene glycol copolymers, including ethylene oxide-propylene oxide (“EO/PO”) copolymers and butyl alcohol-ethylene oxide-propylene oxide copolymers. The weight average molecular weight of the suppressors may range from 800-15000, preferably from 1000 to 15,000. When such suppressors are used, they are preferably present in a range of 0.5 g/L to 15 g/L based on the weight of the composition, and more preferably from 1 g/L to 5 g/L.

In general, the reaction products have a number average molecular weight (Mn) of 200 to 125,000, typically from 1000 to 75,000, preferably from 1500 to 10,000, although reaction products having other Mn values may be used. Such reaction products may have a weight average molecular weight (Mw) value in the range of 1000 to 500,000, typically from 10,000 to 30,000, although other Mw values may be used.

The amount of the reaction product used in the copper electroplating baths for plating photoresist defined features, preferably copper pillars, may range from 0.25 ppm to 1000 ppm, preferably from 0.25 ppm to 500 ppm, more preferably from 5 ppm to 500 ppm, based on the total weight of the plating bath.

The electroplating baths may be prepared by combining the components in any order. It is preferred that the inorganic components such as source of metal ions, water, electrolyte and optional halide ion source are first added to the bath vessel, followed by the organic components such as leveling agent, accelerator, suppressor, and any other organic component.

The aqueous copper electroplating baths may optionally contain a conventional leveling agent provided such the leveling agent does not substantially compromise the morphology of the copper features. Such leveling agents may include those disclosed in U.S. Pat. No. 6,610,192 to Step et al., U.S. Pat. No. 7,128,822 to Wang et al., U.S. Pat. No. 7,374,652 to Hayashi et al. and U.S. Pat. No. 6,800,188 to Hagiwara et al. However, it is preferred that such leveling agents are excluded from the baths.

Typically, the plating baths may be used at any temperature from 10 to 65° C. or higher. Preferably, the temperature of the plating composition is from 15 to 50° C. and more preferably from 20 to 40° C.

In general, the copper electroplating baths are agitated during use. Any suitable agitation method may be used and such methods are well-known in the art. Suitable agitation methods include, but are not limited to: air sparging, work piece agitation, and impingement.

Typically, a substrate is electroplated by contacting the substrate with the plating bath. The substrate typically functions as the cathode. The plating bath contains an anode, which may be soluble or insoluble. Potential is applied to the electrodes. Current densities may range from 0.25 ASD to 40 ASD, preferably 1 ASD to 30 ASD, more preferably from 10 ASD to 30 ASD.

While the method of the present invention may be used to electroplate photoresist defined features such as pillars, bonding pads and line space features, the method is described in the context of plating copper pillars which is the preferred feature of the present invention. Typically, the copper pillars may be formed by first depositing a conductive seed layer on a substrate such as a semiconductor chip or die. The substrate is then coated with a photoresist material and imaged to selectively expose the photoresist layer to radiation such as UV radiation. The photoresist layer may be applied to a surface of the semiconductor chip by conventional processes known in the art. The thickness of the photoresist layer may vary depending on the height of the features. Typically the thickness ranges from 1 μm to 250 μm. A patterned mask is applied to a surface of the photoresist layer. The photoresist layer may be a positive or negative acting photoresist. When the photoresist is positive acting, the portions of the photoresist exposed to the radiation are removed with a developer such as an alkaline developer. A pattern of a plurality of apertures such as vias is formed on the surface which reaches all the way down to the seed layer on the substrate or die. The pitch of the pillars may range from 20 μm to 400 μm. Preferably the pitch may range from 100 μm to 350 μm. The diameters of the vias may vary depending on the diameter of the feature. The diameters of the vias may range from 2 μm to 300 μm, typically from 50 μm to 225 μm. The entire structure may then be placed in a copper electroplating bath containing one or more of the reaction products of the present invention. Electroplating is done to fill at least a portion of each via with a copper pillar with a substantially flat top. The electroplating is conformal or same plating speed everywhere deposition, not super-conformal or superfilling. The entire structure with the copper pillars is then transferred to a bath containing solder, such as a tin solder or tin alloy solder such as a tin/silver or tin/lead alloy and a solder bump is electroplated on the substantially flat surface of each copper pillar to fill portions of the vias. The remainder of the photoresist is removed by conventional means known in the art leaving an array of copper pillars with solder bumps on the die. The remainder of the seed layer not covered by pillars is removed through etching processes well known in the art. The copper pillars with the solder bumps are placed in contact with metal contacts of a substrate such as a printed circuit board, another wafer or die or an interposer which may be made of organic laminates, silicon or glass. The solder bumps are heated by conventional processes known in the art to reflow the solder and join the copper pillars to the metal contacts of the substrate. Conventional reflow processes for reflowing solder bumps may be used. An example of a reflow oven is FALCON 8500 tool from Sikiama. International, Inc. which includes 5 heating and 2 cooling zones. Reflow cycles may range from 1-5. The copper pillars are both physically and electrically contacted to the metal contacts of the substrate. An underfill material may then be injected to fill space between the die, the pillars and the substrate. Conventional underfills which are well known in the art may be used.

FIGS. 1 and 2 are SEMs of copper pillars of the present invention having cylindrical morphology with a base and sufficiently flat top for electroplating solder bumps. During reflow solder is melted to obtain a smooth surface. If pillars are too domed during reflow, the solder may melt and flow off the sides of the pillar and then there is not enough solder on the top of the pillar for subsequent bonding steps. If the pillar is too dished as shown in FIG. 3, material left from the copper bath which was used to electroplate the pillar may be retained in the dished top and contaminate the solder bath, thus shortening the life of the solder bath.

To provide a metal contact and adhesion between the copper pillars and the semiconductor die during electroplating of the pillars, an underbump metallization layer typically composed of a material such as titanium, titanium-tungsten or chromium is deposited on the die. Alternatively, a metal seed layer, such as a copper seed layer, may be deposited on the semiconductor die to provide metal contact between the copper pillars and the semiconductor die. After the photosensitive layer has been removed from the die, all portions of the underbump metallization layer or seed layer are removed except for the portions underneath the pillars. Conventional processes known in the art may be used.

While the height of the copper pillars may vary, typically they range in height from 1 μm to 300 μm, preferably from 20 μm to 250 μm, more preferably from 50 μm to 225 μm. Diameters of the copper pillars may also vary. Typically the copper pillars have a diameter of 2 μm to 300 μm, preferably from 20 μm to 250 μm, more preferably 50 μm to 225 μm.

The copper electroplating methods and baths provide copper photoresist defined features which have a substantially uniform morphology and are substantially free of nodules. The copper pillars and bond pads have a substantially flat profile. The copper electroplating baths and methods enable an average % TIR to achieve the desired morphology as well as a balance between an average % TIR and % WID.

The following examples are intended to further illustrate the invention but are not intended to limit its scope.

Example 1

3,5-Dimethylpyrazole (0.1 mol) and DI water (20 mL) were added into round-bottom flask equipped with a magnetic stirrer and thermometer. The reaction flask was placed in a heating bath set to 95° C. When internal temperature reached 80° C., glycerol diglycidyl ether (0.063 mol) was added dropwise using an addition funnel. After addition was completed, the reaction mixture was stirred for 2 hours with oil bath set at 110° C. 5.6 g of 50% sulfuric acid was added to clarify the emulsion. The reaction mixture was stirred for an additional 3 hours and then cooled down to room temperature. The final product was transferred to a storage container. Reaction product 1 was used without purification.

Example 2

An aqueous acid copper electroplating bath was prepared by combining 60 g/L copper ions from copper sulfate pentahydrate, 60 g/L sulfuric acid, 90 ppm chloride ion, 12 ppm of an accelerator and 2 g/L of a suppressor. The accelerator was bis(sodium-sulfopropyl)disulfide. The suppressor was an EO/PO copolymer having a weight average molecular weight of 1,000 and terminal hydroxyl groups. The electroplating bath also contained 100 ppm of reaction product 1 from Example 1. The pH of the bath was less than 1.

A 300 mm silicon wafer segment with a patterned photoresist 240 μm thick and a plurality of apertures (available from IMAT, Inc., Vancouver, Wash.) was immersed in the copper electroplating bath. The anode was a soluble copper electrode. The wafer and the anode were connected to a rectifier and copper pillars were electroplated on the exposed seed layer at the bottom of the apertures. The aperture diameters were 200 μm. Average current density during plating was 27 ASD and the temperature of the copper electroplating bath was at 45° C. After electroplating the remaining photoresist was then stripped with BPR photostripper solution available from the Dow Chemical Company leaving an array of copper pillars on the wafer. Eight copper pillars were then analyzed for their morphology. The heights and TIR of the pillars were measured using an optical white light LEICA DCM 3D microscope. The % TIR was determined by the following equations:

% TIR=[height_(center)−height_(edge)]/height_(max)×100,

TIR=height_(center)−height_(edge)

The average % TIR of the eight pillars was also determined as shown in the table.

TABLE 1 Pillar Height_(max) Pillar # Pitch (μm) (μm) Pillar TIR (μm) % TIR 1 395 213.6 11.2 5.3 2 395 196.9 11.9 5.7 3 395 203.4 10.4 4.9 4 395 212.4 9.6 4.3 5 395 211.8 8.8 4.0 6 395 204.5 10.5 4.9 7 395 198.3 9.3 4.5 8 395 203.8 10.1 4.7 Avg. — 214.0 10.2 4.8% The % WID for the array of pillars was determined with the optical white light LEICA DCM 3D microscope and the following equation: % WID = ½ × [(height_(max) − height_(min))/height_(avg)] × 100

The % WID was 3.5% and the average % TIR was 4.8%. The surface of the pillars all appeared smooth and free of nodules. The copper electroplating bath which included reaction product 1 plated very good copper pillars. FIG. 1 is a 300× AMRAY SEM image of one of the pillars plated on a seed layer and analyzed with the optical microscope. The surface morphology was smooth and flat on top for receiving solder.

Example 3

3,5-Dimethylpyrazole (0.1 mol) and DI water (20 mL) were added into round-bottom flask equipped with a magnetic stirrer and thermometer. The reaction flask was placed in a heating bath set to 95° C. When internal temperature reached 80° C., neopentyl glycol diglycidyl ether (0.1 mot) was added dropwise using an addition funnel. After addition was completed, the reaction mixture was stirred for 2 hours with oil bath set at 110° C. 5.6 g of 50% sulfuric acid was added to clarify the emulsion. The reaction mixture was stirred for an additional 3 hours and then cooled down to room temperature. The final product was transferred to a storage container. Reaction product 2 was used without purification.

Example 4

An aqueous acid copper electroplating bath was prepared by combining 50 g/L copper ions from copper sulfate pentahydrate, 120 g/L sulfuric acid, 50 ppm chloride ion, 60 ppm of an accelerator and 0.5 g/L of a suppressor. The accelerator was bis(sodium-sulfopropyl)disulfide. The suppressor was an EO/PO copolymer having a weight average molecular weight of 1,000 and terminal hydroxyl groups. The electroplating bath also contained 200 ppm of reaction product 2 from Example 3. The pH of the bath was less than 1.

A 300 mm silicon wafer segment having two different pitches, a dense area and a sparse area of 100 μm and 250 μm, respectively, with a patterned photoresist 50 μm thick and a plurality of apertures (available from Inc., Vancouver, Wash.) was immersed in the copper electroplating bath. The anode was a soluble copper electrode. The wafer and the anode were connected to a rectifier and copper pillars were electroplated on the exposed seed layer at the bottom of the apertures. The aperture diameters were 50 μm. Average current density during plating was 20 ASD and the temperature of the copper electroplating bath was at 25° C. After electroplating the remaining photoresist was then stripped with BPR photostripper solution available from the Dow Chemical Company leaving an array of copper pillars on the wafer. Eight copper pillars for each pitch were then analyzed for their morphology. The data for both the TIR and the % WID are collected across all three pitches. The heights and TIR of the pillars were measured using a KEYENCE 3D Laser Scanning Confocal Microscope VK-X Series. The % TIR was determined by the following equations:

% TIR=[height_(center)−height_(edge)]/height_(max)×100,

TIR=height_(center)−height_(edge)

The average % TIR of the eight pillars was also determined as shown in the table.

TABLE 2 Variable Pillar Height_(max) Pillar # Pitches (μm) (μm) Pillar TIR (μm) % TIR 1 100 33.9 2.4 7.1 2 100 33.5 3.1 9.2 3 100 31.4 2.8 8.9 4 100 31.0 3.8 12.2 5 100 31.2 4.1 13.1 6 250 32.9 1.7 5.2 7 250 32.6 2.0 6.1 8 250 32.3 2.9 9.0 Avg. — 32.4 2.9 8.9% The % WID for the array of pillars was determined with a KEYENCE 3D Laser Scanning Confocal Microscope VK-X Series and the following equation: % WID = ½ × [(height_(max) − height_(min))/height_(avg)] × 100

The % WID was 4.5% and the average % TIR was 8.9%. The surface of the pillars all appeared smooth and free of nodules. The copper electroplating bath which included reaction product 2 plated very good copper pillars. FIG. 2 is an image of one of the pillars plated on a seed layer and analyzed using the 3D image collected using a KEYENCE 3D Laser Scanning Confocal Microscope VK-X Series. The surface morphology was smooth and flat on top for receiving solder.

Example 5 (Comparative)

In a 125 ml, round-bottom, three-neck flask equipped with a condenser and a thermometer, 90 mmol of 2-methylquinolin-4-amine, 10 mmol of 2-(2-aminoethyl)pyridine were added into a mixture of 20 mL of DI water and 5 ml of 50% sulfuric acid. The mixture was heated to 80° C. followed by drop wise addition of 100 mmol of 1,4-butanediol diglycidyl ether. The resulting mixture was heated for about 4 hours using an oil bath set to 95° C. and then left to stir at room temperature for an additional 8 hours. The reaction product (reaction product 3-comparative) was diluted using acidified water and used without further purification.

Example 6 (Comparative)

The method described in Example 2 was repeated with the same copper electroplating bath, wafer and plating parameters except reaction product 3-comparative was substituted for reaction product 1. Reaction product 3-comparative was included in the copper electroplating bath in an amount of 1 ppm. After the wafer was plated with pillars, the photoresist was stripped leaving an array of copper pillars on the silicon wafer. The pillars appeared rough and many had “sink-hole” centers as shown in FIG. 3. The % WED and average % TIR were not calculated. The pillars were very defective, thus the profilometer was unable to read them accurately. 

What is claimed is:
 1. A method comprising: a) providing a substrate comprising a layer of photoresist, wherein the layer of photoresist comprises a plurality of apertures; b) providing a copper electroplating bath comprising one or more reaction products of one or more pyrazole compounds and one or more bisepoxides; an electrolyte; one or more accelerators; and one or more suppressors; c) immersing the substrate comprising the layer of photoresist with the plurality of apertures in the copper electroplating bath; and d) electroplating a plurality of copper photoresist defined features in the plurality of apertures, the plurality of photoresist defined features comprise an average % TIR of 0% to 10%.
 2. The method of claim 1, wherein a % WID of the plurality of photoresist defined features is from 0% to 10%.
 3. The method of claim 1, wherein the one or more pyrazole compounds have a formula:

where R₁, R₂ and R₃ are independently chosen from hydrogen, linear or branched (C₁-C₁₀)alkyl; hydroxyl; linear or branched (C₁-C₁₀)alkoxy; linear or branched hydroxy(C₁-C₁₀)alkyl; linear or branched alkoxy(C₁-C₁₀)alkyl; linear or branched, carboxy(C₁-C₁₀)alkyl, linear or branched amino(C₁-C₁₀)alkyl; and substituted or unsubstituted phenyl.
 4. The method of claim 1 wherein the one or more bisepoxides are chosen from compounds having formula:

wherein R₄ and R₅ may be the same or different and are chosen from hydrogen and (C₁-C₄)alkyl; R₆ and R₇ may be the same of different and are chosen from hydrogen, methyl and hydroxyl; m=1-6 and n=1-20.
 5. The method of claim 1, wherein the reaction product is in amounts of 0.25 ppm to 1000 ppm.
 6. The method of claim 1, wherein electroplating is done at a current density of 0.25 ASD to 40 ASD.
 7. The method of claim 1, wherein the one or more copper photoresist defined features are pillars, bond pads or line space features.
 8. An array of photoresist defined features on a substrate comprising an average % TIR of 0% to 10% and a % WID of 0% to 10%. 